WO2007029551A1

WO2007029551A1 - Organic thin film transistor, base body for organic thin film transistor and method for manufacturing organic thin film transistor

Info

Publication number: WO2007029551A1
Application number: PCT/JP2006/316907
Authority: WO
Inventors: Katsura Hirai; Chiyoko Takemura
Original assignee: Konica Minolta Holdings, Inc.
Priority date: 2005-09-08
Filing date: 2006-08-29
Publication date: 2007-03-15
Also published as: JPWO2007029551A1

Abstract

Provided are an organic thin film transistor, which has excellent TFT characteristics and is manufactured by a solution process having a high production efficiency, and a method for manufacturing such organic thin film transistor. The organic thin film transistor is provided with a base body and an organic semiconductor layer on the surface of the base body. The organic thin film transistor is characterized in that a surface finished layer is formed on the base body surface between the organic semiconductor layer and the base body by using 2-5 kinds of surface finishing agents.

Description

Specification

Organic thin film transistor, organic thin film transistor substrate, and organic thin film transistor manufacturing method

Technical field

TECHNICAL FIELD [0001] The present invention relates to an organic thin film transistor substrate for organic thin film transistor and a method for producing an organic thin film transistor.

Background art

With the widespread use of information terminals, there is an increasing need for flat panel displays as computer displays. In addition, with the progress of computerization, information that has been provided on paper media in the past has been digitized and provided more and more. As a display medium for mopile that is thin, light, and easy to carry, electronic paper or The need for digital paper is also increasing.

In general, in a flat panel display device, a display medium is formed using elements utilizing liquid crystal, organic EL, electrophoresis or the like. In such display media, in order to ensure uniformity of screen brightness, screen rewriting speed, and the like, a technique using an active drive element composed of a thin film transistor (TFT) as an image drive element has become mainstream. For example, in a normal computer display, these TFT elements are formed on a glass substrate, and liquid crystals, organic EL elements, etc. are sealed.

[0004] Here, a TFT element usually has a semiconductor thin film such as a-Si (amorphous silicon) or p-Si (polysilicon) or a metal thin film such as a source, drain, or gate electrode on a glass substrate. It is manufactured by sequentially forming on the substrate. The production of flat panel displays using TFTs usually requires high-precision photolithographic processes in addition to vacuum equipment such as CVD and sputtering and thin film formation processes that require high-temperature processing processes. The running cost is very heavy. Furthermore, with the recent increase in the screen size of displays, their costs have become enormous.

[0005] Further, since the formation of such a conventional TFT element using a Si material involves a process at a high temperature, the substrate material is subject to a limitation on being a material that can withstand the process temperature. become. For this reason, in practice, glass must be used, and when the above-mentioned electronic paper or digital paper! /, And a thin display using such a conventionally known TFT element are used, the display Will be heavy and inflexible, and may be broken by the impact of a drop. These characteristics resulting from the formation of TFT elements on a glass substrate are desirable in satisfying the need for easy-to-use thin displays with the progress of computerization.

[0006] On the other hand, in recent years, organic semiconductor materials have been energetically studied as organic compounds having high charge transport properties, and application to organic thin film transistors is expected. If these organic semiconductor devices can be realized, solution can be obtained by simplifying the manufacturing process by relatively low temperature, vacuuming at low temperature, and low-pressure deposition, and by appropriately improving the molecular structure. It is thought that there is a possibility of obtaining a semiconductor, and the production by a printing method including an ink jet method can be considered by converting an organic semiconductor solution into an ink. Manufacturing using these low-temperature processes has been considered impossible for conventional Si-based semiconductor materials.

There is a possibility for devices using 1S organic semiconductors, so the above-mentioned restrictions on the heat resistance of the substrate are relaxed, and for example, a TFT element may be formed on a transparent resin substrate. If a TFT element can be formed on a transparent resin substrate and the display material can be driven by the TFT element, the display is lighter and more flexible than conventional ones. Will be difficult to crack))

[0007] With respect to a method for producing an organic semiconductor thin film by a solution process, for example, a method using a liquid crystalline material as a solvent of an organic semiconductor material as in Patent Document 1 and a fluorination as in Patent Document 2 A method of manufacturing on a surface substrate is disclosed. Patent Document 3 discloses a method of using a mixed solvent for the production of an organic semiconductor thin film.

[0008] The surface of the substrate on which the organic semiconductor layer is formed is generally subjected to surface treatment with octadecyltrichlorosilane, HMDS or the like before the organic semiconductor layer is formed. Patent Document 4 discloses surface treatment of a gate insulating film with a surface treatment material containing a phenyl group or the like.

[0009] A silane coupling agent having an alkyl group or a phenyl group on the surface of the substrate while exerting force When surface treatment is performed by itself, the performance of the organic thin film transistor device (TFT device) in which the organic semiconductor layer is created by the vapor deposition process is improved, but the surface of the substrate created by the solution process repels the organic semiconductor solution. As a result, it was difficult to provide a stable organic semiconductor layer with insufficient coating properties. Therefore, it is desirable for the solution process to achieve both TFT characteristics and coating properties of organic semiconductor materials. Patent Document 1: Japanese Patent Laid-Open No. 2004-31458

Patent Document 2: JP 2000-307172 A

Patent Document 3: International Publication No. 03Z65409 Pamphlet

Patent Document 4: Japanese Patent Laid-Open No. 2005-158765

Disclosure of the invention

Problems to be solved by the invention

[0010] The present invention has been made in view of the above problems, and an object of the present invention is to provide an organic thin film transistor manufactured by a solution process having good TFT characteristics and high production efficiency, and a method for manufacturing the same.

Means for solving the problem

The above object of the present invention has been achieved by the following constitution.

1. An organic thin film transistor having a substrate and an organic semiconductor layer on the surface thereof, and having a surface treatment layer formed of 2 to 5 kinds of surface treatment agents on the substrate surface between the organic semiconductor layer and the substrate. Organic thin-film transistor characterized.

2. The organic thin film transistor according to 1 above, wherein the surface treatment agent is a silane compound.

3. The organic thin film transistor as described in 2 above, wherein at least one of the surface treatment agents is a silane compound having an alkyl group.

4. The organic thin film transistor as described in 2 above, wherein at least one of the surface treatment agents is a silane compound having an aromatic group.

5. The organic thin film transistor according to 2 above, wherein at least one of the surface treatment agents is a silane compound having an alkyl group, and at least one is a silane compound having an aromatic group. 6. The organic thin film transistor substrate according to any one of 1 to 5 above, wherein a contact angle with respect to water of the surface of the surface-treated substrate is 50 degrees or more.

7. The organic thin film transistor according to any one of 1 to 5, wherein the organic semiconductor material contained in the organic semiconductor layer has an alkyl group.

8. The organic thin film transistor according to any one of 1 to 5 and 7, wherein the organic thin film transistor has a bottom gate structure.

9. The method for producing an organic thin film transistor according to any one of 1 to 5, 7, and 8, wherein the surface treatment is performed by supplying a solution of the surface treatment agent to the surface of the substrate. Manufacturing method of organic thin-film transistor.

10. The method for producing an organic thin film transistor according to any one of 1 to 5, 7, and 8, wherein the surface treatment is performed by a plasma CVD method using the surface treatment agent. Method.

11. The method for producing an organic thin film transistor as described in 10 above, wherein the plasma CVD method is an atmospheric pressure plasma CVD method.

12. An organic thin film transistor produced by the method for producing an organic thin film transistor according to any one of 9 to 11 above.

The invention's effect

The present invention can provide an organic thin film transistor manufactured by a solution process having good TFT characteristics and high production efficiency, and a method for manufacturing the same.

Brief Description of Drawings

FIG. 1 is a conceptual diagram showing an example of a plasma discharge treatment container.

FIG. 2 is a schematic view showing another example of a plasma discharge treatment container.

FIG. 3 is a schematic perspective view showing an example of a cylindrical roll electrode.

FIG. 4 is a schematic perspective view showing an example of a cylindrical fixed electrode.

FIG. 5 is a schematic perspective view showing an example of a prismatic fixed electrode.

FIG. 6 is a conceptual diagram showing an example of a plasma discharge treatment apparatus.

FIG. 7 is a schematic view showing another example of a plasma discharge treatment apparatus.

FIG. 8 is a schematic view showing an example of an atmospheric pressure plasma discharge treatment apparatus. FIG. 9 is a schematic view showing another example of an atmospheric pressure plasma discharge treatment apparatus.

FIG. 10 is a diagram showing an example of the configuration of an organic thin film transistor element.

Explanation of symbols

[0014] 20 Plasma discharge treatment vessel

40 Gas generator

51 Organic semiconductor layer

52 Source electrode

53 Drain electrode

54 Gate electrode

55 Insulation layer

60 original winding substrate

P atmospheric pressure plasma discharge treatment equipment

F substrate

G discharge gas

M Thin film forming gas

BEST MODE FOR CARRYING OUT THE INVENTION

As a result of intensive studies in view of the above problems, the present inventors have found that the carrier mobility is improved by increasing the contact angle of the layer in contact with the organic semiconductor layer (substrate surface). Apply at least two types of surface treatment agent to the surface of the surface of the surface of the coating to improve the coating properties.

The present inventors have found that an organic thin film transistor can be manufactured by a solution process capable of achieving both TFT device performance and high production efficiency.

Hereinafter, the present invention will be described in detail.

[Surface treatment agent]

In the present invention, the surface of the substrate (both substrate !, u) is subjected to surface treatment using 2 to 5 types of surface treatment agents to form a surface treatment layer on the surface of the substrate, and then the surface treatment layer is coated on the surface treatment layer. It is characterized by forming an organic semiconductor layer.

[0017] As the surface treating agent used in the present invention, an agent that increases the contact angle of the surface with water when the surface of the substrate is surface treated is used. Against surface water after surface treatment The contact angle is preferably 50 degrees or more, more preferably 70 to 170 degrees, and even more preferably 90 to 130 degrees. If the contact angle is low, the carrier mobility and onZoff ratio of the transistor element are remarkably lowered, and if it is too high, the coating property of the organic semiconductor material solution is lowered. This contact angle is measured using a contact angle meter (CA-DT, type A: manufactured by Kyowa Interface Science Co., Ltd.) in an environment of 20 ° C 50% RH.

[0018] By forming the surface treatment layer, it is effective that an alkyl group or an aromatic group is present on the outermost surface of the substrate. Accordingly, it is preferable that the surface treatment agent has an alkyl group or an aromatic group. The alkyl group may be a fluoroalkyl group or an alkyl group composed only of carbon and hydrogen. The alkyl group has 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms. Examples of the aromatic group include an aromatic hydrocarbon group having 6 to 20 carbon atoms such as a phenyl group which may have a substituent. More preferably, an organosilane compound having both a hydrolyzable group and an alkyl group is used.

Here, the hydrolyzable group means a functional group that can be polymerized by adding water and hydrogen, and is not particularly limited in the present invention, but preferably an alkoxy group or an acetyl group. Can be mentioned. More preferably, it is an alkoxy group, and further preferably has an ethoxy group in terms of reactivity and physical properties of the raw material.

[0020] In addition to the organosilane compound, an organometallic compound in which the metal element is Ti, Ge, Zr or Sn, and a compound having fluorine are also particularly preferred. An organosilane compound, Ti is particularly preferred. And a compound having fluorine.

Specifically, a compound represented by the following general formula (1) is preferable.

[0022] [Chemical formula 1] General formula (1)

In the general formula (1), M represents Si, Ti, Ge, Zr or Sn. R to R are each

1 6 represents a hydrogen atom or a monovalent group, R to R

At least one of the groups represented by 16 is an organic group having a fluorine atom, such as an alkyl group or alkenyl group having a fluorine atom. Examples of the alkyl group having a fluorine atom that is preferable for an organic group containing an aryl group include, for example, a trifluoromethyl group, a perfluoroethyl group, and a perfluoropropyl group.

, Perfluorobutyl group, 4, 4, 3, 3, 2, 2, 1, 1-octafluorobutyl group, etc. As the alkenyl group having a fluorine atom, for example, 3, 3, 3-Trifluoro-1-propenyl group and the like Further, the aryl group having a fluorine atom includes groups such as a pentafluorophenyl group. In addition, an alkyl group having a fluorine atom, an alkyl group, an alkoxy group formed by an aryl group, an alkyl group, an aryloxy group, or the like can also be used.

[0024] In addition, any number of fluorine atoms may be bonded to any position of the carbon atom in the skeleton, such as at least one or more of the alkyl group, alkenyl group, aryl group, and the like. Bonding is preferred. In addition, the carbon atom in the skeleton of the alkyl group or alkenyl group includes, for example, other atoms such as oxygen, nitrogen and sulfur, and divalent groups containing oxygen, nitrogen and sulfur, such as a carbonyl group and a thiocarbonyl group. It may be substituted with a group.

[0025] Among the groups represented by R to R, except for the organic group having a fluorine atom, a hydrogen atom or

1 6

Represents a monovalent group, and examples of the monovalent group include a hydroxy group, an amino group, an isocyanate group, a halogen atom, an alkyl group, a cycloalkyl group, a alkenyl group, an aryl group, an alkoxy group, and an alkenyl group. Forces including groups such as a ruoxy group and an aryloxy group, but are not limited thereto. j represents an integer of 0 to 150, preferably 0 to 50, and more preferably j is in the range of 0 to 20.

[0026] Among the monovalent groups, the halogen atom is preferably a chlorine atom, a bromine atom or an iodine atom. Among the monovalent groups, the alkyl group, alkyl group, aryl group, alkoxy group, alkoxy group, and aryloxy group are preferably an alkoxy group, an alkoxy group, and an aryloxy group. is there.

[0027] Of the metal atoms represented by M, Si and Ti are preferable.

[0028] The monovalent group may be further substituted with another group, but is not particularly limited. Preferred substituents include amino group, hydroxyl group, isocyanate group, fluorine atom, chlorine atom, bromine. Halogen atoms such as atoms, alkyl groups, cycloalkyl groups, alkenyl groups, phenyl groups such as phenyl groups, alkoxy groups, alkoxy groups, aryloxy groups And groups such as an acyl group, an acyloxy group, an alkoxycarbonyl group, an alkanamide group, an arylamide group, an alkyl group rubamoyl group, an aryl group rubamoyl group, a silyl group, an alkylsilyl group, and an alkoxysilyl group.

[0029] In addition, the organic group having a fluorine atom, or represented by these other R R

1 6 group is RiR ² R ³ M— (M represents the metal atom,

R ³ each represents a monovalent group, and examples of the monovalent group include the organic group having a fluorine atom or RR.

1 6

Represents a group other than the organic group having a fluorine atom. Or a structure having a plurality of metal atoms further substituted by a group represented by Examples of these metal atoms include Si Ti and the like, and examples thereof include a silyl group, an alkylsilyl group, and an alkoxysilyl group.

[0030] R R! /, An alkyl group which is a group having a fluorine atom,

1 6

As the -alkyl group, the alkoxy group formed by these forces, the alkyl group in the alkyloxy group, and the alkyl group, a group represented by the following general formula (F) is preferable.

[0031] General formula (F)

Rf— X— (CH) —

2k

Here, Rf represents an alkyl group or an alkenyl group in which at least one of hydrogen is substituted with a fluorine atom, and examples thereof include a trifluoromethyl group, a pentafluoroethyl group, a perfluorooctyl group, and a heptafluoropropyl group. Groups such as perfluoroalkyl groups, 3, 3, 3 trifluoropropyl groups, 4, 4, 3, 3, 2, 2, 1, 1-octafluorobutyl groups, Among those preferred are alkenyl groups substituted by fluorine atoms such as 1, 1, 1 trifluoro-2-chloroprobe group, trifluoromethyl group, pentafluoroethyl group, perfluoro group, etc. Loctyl group, heptafluoropropyl group, etc., and 3, 3, 3 trifluoropropyl group, 4, 4, 3, 3, 2, 2, 1, 1—octafluorobutyl group, etc. An alkyl group having two or more fluorine atoms Masui.

[0032] X is a simple bond or a divalent group. As a divalent group, —O— — S

Groups such as NR— (where R represents a hydrogen atom or an alkyl group), CO——CO—O——CONH SO NH SO—O OCONH

twenty two

[0033] [Chemical 2] O CCCIII

[0034] represents a group such as

[0035] k represents an integer of 0 to 50, preferably 0 to 30.

[0036] In Rf, in addition to the fluorine atom, other substituents that may be substituted may be the same groups as those exemplified as the substituents in R to R. Can be mentioned. Ma

1 6

In addition, the skeletal carbon atom in Rf is another atom, for example, O—, — S—, —NR— (R is hydrogen

0 0 represents an atom or a substituted or unsubstituted alkyl group, and may be a group represented by the general formula (F)), a carbo group, one NHCO, one CO—O, one SO NH, etc. of

2

It may be partially substituted by a group.

[0037] Of the compounds represented by the general formula (1), the compounds represented by the following general formula (2) are preferable.

[0038] General formula (2)

[Rf— X— (CH)] M (R) (OR)

2 k q 10 r 11 t

In general formula (2), M represents the same metal atom as in general formula (1), Rf and X represent the same groups as Rf and X in general formula (F), and k represents the same integer. To express. R is a

10 represents an alkyl group, an alkenyl group, or R represents an alkyl group, an alkenyl group, or an aryl group.

11

Respectively, by the same groups as those mentioned as the substituents for R 1 to R in the general formula (1).

1 6

Although it may be substituted, it preferably represents an unsubstituted alkyl group or alkenyl group. Also

Q + r + t = 4, q≥l, and t≥l. When r≥2, two Rs are connected to form a ring.

Ten

May be formed.

[0039] Of the general formula (2), more preferred is a compound represented by the following general formula (3).

[0040] General formula (3)

Rf— X— (CH) — M (OR)

2 k 12 3

In the general formula (3), Rf, X, or k has the same meaning as in the general formula (2). R is also synonymous with R in the general formula (2). M is also represented by the general formula (2).

12 11

It is the same as M in the above, but in particular, Si is the most preferable Si and Ti are preferable.

[0041] In the present invention, other preferable examples of organometallic compounds having a fluorine atom, for example, compounds represented by the following general formula (4) are mentioned.

[0042] [Chemical formula 3] General formula << 4

[0043] In the general formula (4), M and R to R have the same meanings as R to R in the general formula (1).

1 6 1 6 Also in this case, at least one of R to R is an organic group having the fluorine atom.

1 6

And the group represented by the general formula (F) is preferable. R is a hydrogen atom, or substituted or

7

Represents an unsubstituted alkyl group. J represents an integer of 0 to: L00, preferably 0 to 50, and most preferably j is in the range of 0 to 20.

[0044] Another preferred compound having a fluorine atom used in the present invention is an organometallic compound having a fluorine atom represented by the following general formula (5).

[0045] General formula (5)

[Rf-X- (CH) -Y] M (R) (OR)

2 km 8 n 9 p

In the general formula (5), M represents In, Al, Sb, Y or La. Rf and X represent the same groups as Rf and X in the general formula (F 1), and Y represents a simple bond or oxygen. k also represents an integer of 0 to 50, preferably an integer of 30 or less. R is an alkyl group or

9

Represents an alkenyl group, and R represents an alkyl group, an alkenyl group or an aryl group.

8

Each of R to R in the general formula (1)

It may be substituted with a group similar to the group listed as the substituent of 16. In the general formula (5), m + n + p = 3, m is at least 1, n is 0 to 2, and p is an integer of 0 to 2. It is preferable that m + p = 3, that is, n = 0.

[0046] Another preferable example of the compound having a fluorine atom used in the present invention is an organometallic compound having a fluorine atom represented by the following general formula (6). [0047] General formula (6)

R ⁿ (OCF) -O- (CF)-(CH) -Z- (CH) —Si— (R ² )

3 6 ml 2 nl 2 pi 2 ql 3

In the general formula (6), R ⁿ represents a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, R ² represents a hydrolyzable group, Z represents —OCONH or —O, ml represents an integer of 150, nl represents an integer of 0 3, pi represents an integer of 0 3, ql represents an integer of 1 6, and 6≥nl + p 1> 0.

[0048] The number of carbon atoms of the linear or branched perfluoroalkyl group that can be introduced into 1 is more preferably 1 13, and most preferably 1 3. Therefore, R ⁿ is CF CFCF

3 2 5 3 7 etc. are preferable.

[0049] Hydrolyzable groups that can be introduced into R ² include Cl -Br, —1 -OR ¹¹ , —OCOR ^u C 0 (R ⁿ ) C = C (R ¹² ) —ON = C (R ^U ) — ^{ON = CR 13 - N (R} 12) - R 12 NOCR U

2 2 2

Etc. are preferred. R ¹¹ represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms such as an alkyl group, or an aromatic hydrocarbon group having 6 to 20 carbon atoms such as a phenyl group, and R ¹² represents a carbon number such as a hydrogen atom or an alkyl group. 15 represents an aliphatic hydrocarbon of 15; R ¹³ represents a divalent aliphatic hydrocarbon group having 36 carbon atoms such as an alkylidene group. Among these hydrolyzable groups, —OCH—OCH—OCH—OCOCH and —NH are preferable.

3 2 5 3 7 3 2

[0050] More preferably, ml is 1 30 and more preferably 5 20. More preferably, nl is 1 or 2. More preferably, pi is 1 or 2. Also, ql is more preferred to be 1, 3.

[0051] As another preferred compound having U or fluorine atom used in the present invention, there is an organometallic compound having a fluorine atom represented by the following general formula (7).

[0052] [Chemical 4] General formula (7}

Rf— (OCF ₂ CF ₂ CF2) _a — (OCFCF ₂ ) _b — (OCF ₂ ) _c — *

CH,

Y

(OCF ₂ CF ₂ } _d _OCF (CF ₂ ), CH, C-

<CH ₂ ) _m — 卜 (R ²¹ > ₃ — [0053] In the general formula (7), Rf is a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, X is an iodine atom or a hydrogen atom, Y is a hydrogen atom or a lower alkyl group, Z is a fluorine atom or Trifluoromethyl group, R ²¹ represents a hydrolyzable group, R ²² represents a hydrogen atom or an inert monovalent organic group, a, b, c, d are each an integer of 0 to 200, e Is 0 or 1, m and n are integers from 0 to 2, and p is an integer from 1 to 10.

In the general formula (7), Rf is usually a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, preferably a CF group, a CF group, or a CF group. In Y

3 2 5 3 7

As a lower alkyl group, a C1-C5 thing is normally mentioned.

[0055] R ²¹ hydrolyzable groups include chlorine atoms, bromine atoms, iodine atoms and other halogen atoms, R ²³⁰ groups, R ²³ COO groups, (R ²⁴ ) C = C (R ²³ ) CO groups , (R ²³ ) C = NO group, R ²⁵ C = N

twenty two

O groups, (R ²⁴ ) N groups, and R ²³ CONR ²⁴ groups are preferred. Where R ²³ is usually an alkyl group or the like

2

Is usually an aromatic hydrocarbon group having 6 to 20 carbon atoms such as an aliphatic hydrocarbon group or a phenyl group having 1 to 10 carbon atoms, and R ²⁴ is usually an alkyl group having 1 to 5 carbon atoms such as a hydrogen atom or an alkyl group. A lower aliphatic hydrocarbon group, R ²⁵ is a divalent aliphatic hydrocarbon group usually having 3 to 6 carbon atoms such as an alkylidene group. More preferably, a chlorine atom, CH 2 O

3 groups, C H O

2 5 units, C H O

3 7 units.

[0056] R ²² is a hydrogen atom or an inert monovalent organic group, preferably a monovalent hydrocarbon group usually having 1 to 4 carbon atoms such as an alkyl group. a, b, c and d are integers of 0 to 200, preferably 1 to 50. m and n are integers of 0 to 2, preferably 0. p is an integer of 1 or 2 or more, preferably an integer of 1 to 10, and more preferably an integer of 1 to 5. The number average molecular weight is 5 × 10 ² to 1 × 10 ⁵ , preferably 1 × 10 ³ to 1 × 10 ⁴ .

[0057] Further, as a preferred structure of the silane compound represented by the general formula (7), Rf is C

F group, a is an integer from 1 to 50, b, c and d are 0, e is 1, Z is fluorine

3 7

It is a compound that is an atom and has n force ^.

[0058] In the present invention, the organometallic compound having an organic group having fluorine, which is preferably used as the silane compound having a fluorine atom, and the compounds represented by the general formulas (1) to (7) are typical. Specific compounds are listed below, but the present invention is limited to these compounds. Not.

1: (CF CH CH) Si

3 2 2 4

2: (CF CH CH) (CH) Si

3 2 2 2 3 2

3: (CF CH CH) Si (OCH)

8 17 2 2 2 5 3

4: CH = CH Si (CF)

2 2 3 3

5: (CH = CH COO) Si (CF)

2 2 3 3

6: (CF CH CH) SiCKCH)

3 2 2 2 3

7: CF CH CH Si (CI)

8 17 2 2 3

8: (CF CHCH) Si (OCH)

8 17 2 2 2 2 5 2

9: CF CH CH Si (OCH)

3 2 2 3 3

10: CF CH CH SiCl

3 2 2 3

11: CF (CF) CH CH SiCl

3 2 3 2 2 3

12: CF (CF) CH CH SiCl

3 2 5 2 2 3

13: CF (CF) CH CH Si (OCH)

3 2 5 2 2 3 3 14: CF (CF) CH CH SiCl

3 2 7 2 2 3

15: CF (CF) CH CH Si (OCH)

3 2 7 2 2 3 3 16: CF (CF) CH Si (OCH)

3 2 8 2 2 5 3

17: CF (CH) Si (OCH)

3 2 2 2 5 3

18: CF (CH) Si (OCH)

3 2 2 3 7 3

19: CF (CH) Si (OCH)

3 2 2 4 9 3

20: CF (CF) (CH) Si (OCH)

3 2 5 2 2 2 5 3 21: CF (CF) (CH) Si (OCH)

3 2 5 2 2 3 7 3 22: CF (CF) (CH) Si (OCH)

3 2 7 2 2 2 5 3 23: CF (CF) (CH) Si (OCH)

3 2 7 2 2 3 7 3 24: CF (CF) (CH) Si (OCH) (OCH)

3 2 7 2 2 3 3 7 25: CF (CF) (CH) Si (OCH) OCH

3 2 7 2 2 3 2 3 7 26: CF (CF) (CH) SiCH (OCH)

3 2 7 2 2 3 3 2 27: CF (CF) (CH) SiCH (OC H)

2 7 2 2 2 5 2 P () () () CFCHCHCOCH CH SiOCHI I ϋΊ ϋΊ ϋΊ ϋΊ ϋΊ ϋΊ CCCCC

) OCH

(()) CFOCFCFCF OCF

(()) () () (): CF oCFCFCF o CF CO 77NHCH SiOSioc HCH NHCO

(()) () () () 76: CFCFCFCFOCFCF CONHCH Sioc H I I

() () 75: CF CONHCH siOCH

() 74: CF C ○ NHCH SiCl

() () 73: CF CONHCH siOCH

() () 72: CFCF C H siNCO

() () 71: CFCF CHSiNCO

() () () 70: CFCFc Hc H sioc H

() () () 69: CFCFc Hc H SiCHOCH

() () () 68: CF CFCF CH CH SiCHOCH

() () () 67: CFCFc Hc H siOCH

M

() () () 66: CFOCF oCF CH OCH SiOCH

() () () (61: c H o SiC H NHCOCF oCF oCF CF o CF CONHC H sio

() mll30 = ~

(()) () 60: CFCFCFCFO CF CONHC H Sioc H

() () () 9: CFoc FoCFCHOCH SiOCH ll I II

() () () () 8: CF C HCH siosiCF C HCHll

() () () 7: CF C HCH siosiCHll P () () () 6: CFCHc HCOCH CH Sioc HI l

() () 3is soOCH UN H JI 101: (CF CH) Si-N (CH)

[0060] [Chemical 5]

102

CF ₃ CH _2- ) j-Si— CH ₂ CH ₂ "

103

[0061] In addition,

[0062] [Chemical 6]

104

HHH CF ₃ CH ₂ CH ₂ — Si— N— S 卜 CH ₃

CH, CH

105

[0063] Silazanes such as

106: CF CH— CHTiCl

3 2 2 3

107: CF (CF) CH CH TiCl

3 2 3 2 2 3

108: CF (CF) CH CH Ti (OCH)

3 2 5 2 2 3 3

109: CF (CF) CH CH TiCl

3 2 7 2 2 3

110: Ti (OCF)

3 7 4

111: (CF CH— CH O) TiCl

3 2 2 3 3

112: (CF C H) (CH) Ti O— Ti (CH)

3 2 4 3 2 3 3

Examples thereof include organic titanium compounds having fluorine such as fluorine-containing organic metal compounds as follows.

[0064] 113: CF (CF) CH CH O (CH) GeCl 114: CF (CF) CH CH OCH Ge (OCH)

3 2 3 2 2 2 3 3

115: (C F O) Ge (OCH)

3 7 2 3 2

116: [(CF) CHO] Ge

3 2 4

117: [(CF) CHO] Zr

3 2 4

118: (CFCHCH) Sn (OCH)

3 7 2 2 2 2 5 2

119: (CFCH CH) Sn (OCH)

3 7 2 2 2 5 3

120: Sn (OC F)

3 7 4

121: CF CH CH In (OCH)

3 2 2 3 2

122: In (OCH CHOCF)

2 2 3 7 3

123: Al (OCH CH OC F)

2 2 3 7 3

124: Al (OC F)

3 7 3

125: Sb (OC F)

3 7 3

126: Fe (OCF)

3 7 3

127: Cu (OCH CHOCF)

2 2 3 7 2

128: C F (OC F) 0 (CF) CH OCH Si (OCH)

[0065] [Chemical 7]

129

_{_{_{C 3 F 7 - (OCF;}}} CF 2 CF 2) 24 -0- (CF 2) 2 - -CH 2 CH-

Si- (OCH ₃ ) ₃

[0066] The compounds and the like mentioned in these specific examples are Toray 'Dauco Combining Silicone Co., Ltd., Shinetsu Igaku Kogyo Co., Ltd., Daikin Industries Co., Ltd. (for example, Optool DSX) and Gelest Inc., Solvay Solexis Co., Ltd., etc., and are easily available. For example, J. Fluorine Chem., 79 (1) .87 (1996), Material Technology, 16 ( 5), 209 (199 8), Collect. Czech. Chem. Commun., 44 卷, 750-755, J. Amer. Chem. Soc. 1990, 112 2, 2341-2348, Inorg. Chem. , 10 卷, pages 889-892, 1971, U.S. Pat.No. 3,668,233, Akira Ita, etc., as well as JP-A-58-122979, JP-A-7-242675, JP-A-9-61605, 11-29585, JP 2000-64 It can be produced by the synthesis method described in No. 348, 2000-144097, or the like, or a synthesis method based thereon.

Specific examples of other organic silane compounds preferably used include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltripropoxysilane, methyltributoxysilane, Tiltrimethoxysilane, Ethyltriethoxysilane, Vinyltrimethoxysilane, Vinyltriethoxysilane, Vinyltriacetoxysilane, Vinyltrimethoxyethoxysilane, Phenyltrimethoxysilane, Phenyltriethoxysilane, Phenyltriacetoxysilane , _Ί -black _{propyltrimethoxysilane} , Ί-black propyltriethoxysilane, γ-black propyltriacetoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyl Trimethoxysilane, γ-Aminopropyltriethoxysilane, γ-Mercaptopropyltrimethoxysilane, γ-Mercaptopropyltriethoxysilane, N—j8— (Aminoethyl) -γ-Aminoprovir trimethoxysilane, 13-cyananoethino Retriethoxysilane, Methyltriphenoxysilane, Chloromethyltrimethoxysilane, Chloromethyltriethoxysilane, Glycidoxymethyltrimethoxysilane, Glycidoxymethyltriethoxysilane, a-Glycidchichetiltrimethoxysilane, a-glycidchichetiltriethoxysilane, 13-glycidchichetiltrimethoxysilane, 13-glycidchichetiltriethoxysilane, a-glycidoxypropyltrimethoxysilane, a-glycidoxypropynoletriethoxy Syrah , 13-glycidoxypropyltrimethoxysilane, 13-glycidoxypropinoletriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropinoletriethoxysilane, γ-glycidoxypropyltri _{Propoxysilane} , _Ί -glycidoxypropinoretributoxysilane, _{グリ} -glycidoxyp oral pill trimethoxyethoxysilane, γ-glycidoxypropyltriphenoxysilane, (X-glycidoxybutynoletrimethoxysilane, OL-glycidoxib Tinoletriethoxysilane, 13 Glycidoxybutynoletrimethoxysilane, 13-Glycidoxybutynoletriethoxysilane, γ-Glycidoxybutyltrimethoxysilane, γ-Glycidoxybutyltriethoxysilane, δ-Dalidoxybutyl Trimetoki Sisilane, δ-Dalixoxybutyltriethoxysilane, (3, 4 Epoxycyclohexylene) Methylenotrimethoxysilane, (3, 4-Epoxycyclohexyl) methyltriethoxysilane, j8 (3, 4-Epoxy (Cyclohexyl) ethyltrimethoxy Silane, β- (3, 4-Epoxycyclohexyl) ethyltriethoxysilane, β- (3, 4-Epoxycyclohexenole) ethinoretripropoxysilane, j8 (3, 4-Epoxycyclohexyl) Tiltriboxysilane, _mono (3,4-epoxycyclohexyl) ethyltrimethoxyethoxysilane, _Ύichi (3,4-epoxycyclohexylene) propinoletrimethoxysilane, β- (3,4-epoxycyclo Xyl) etyltriphenoxysilane, γ- (3,4-epoxycyclohexenole) propinoletrimethoxysilane, γ- (3,4-epoxycyclohexyl) propyltriethoxysilane, δ-(3, 4-epoxycyclohexyl) butyltrimethoxysilane and other trialkoxysilanes, triacyloxysilanes, triphenoxysilanes; Toxisilane, phenylenomethinoresin methoxysilane, dimethylenoletoxysilane, phenylmethyljetoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyoxysilane, dimethyldiacetoxysilane, γ- Methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyljetoxysilane, γ mercaptopropylmethyldimethoxysilane, γ mercaptopropylmethyljetoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyljetoxysilane , Methylvinyldimethoxysilene, methylvinyldioxysilane, glycidoxy

Ethoxysilane, α-Glycidoxypropinoremethinoresin methoxysilane, α-Glycidoxip Oral pyrmethyljetoxysilane, 13-Glycidoxypropylmethyldimethoxysilane, 13 Sisilane, γ-Glycidoxypropinoremethinolegetoxysilane Γ-Glycidoxypropinoremethinoresinpropoxysilane, γ-Glycidoxypropenoremethinoresibutoxysilane, γ-Glycidoxypropinoremethinoresimethoxymethoxysilane, γ-Glycidoxypropioxy

Toxisilane, γ-Glycidoxypropylvinyldimethoxysilane, γ-Glycidoxypropylvinyljetoxysilane, γ-Glycidoxypropylphenyldimethoxysilane, γ Dialkoxy silanes such as glycidoxypropyl phenoxy silane, diphenoxy silane, diacinole oxy silane, trimethino ethoxy silane, trimethino methoxy silane, 3, 3, 3-trifluoropropyl trimethoxy silane, dimethoxy methyl 1,3,3-Trifluoroprovir silane, fluoroalkyl silane, hexamethyldisilane, hexamethyldisiloxane, etc., but are not limited to these and may be used alone. Two or more different types can be used simultaneously.

[0068] Among the above compounds, methyltriethoxysilane, etyltriethoxysilane, dimethyldiethoxysilane, dimethylenoresimethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, butyltrimethoxysilane, trimethylethoxysilane and the like are preferable. .

[0069] Further, as another organosilicon compound, a compound represented by the following general formula (8) is used.

[0070] [Chemical 8] General formula (8)

In the general formula (8), n is 0 to 2000. R to R are a hydrogen atom or each

81 88

These are straight-chain, branched or cyclic hydrocarbon groups which may be either saturated or unsaturated, each of which may be the same or different.

[0072] Specifically, it is described in compound catalogs such as a key compound reagent manufactured by Shin-Etsu Chemical Co., Ltd., or Gelest, Inc. Metal-Organics for Material & Polyer Technology in the United States, SILICON C HEMICALS manufactured by Chisso. Among them, those that are suitable for general formula (1) can be selected and used, and the ability to exemplify the compounds that can be used below is, of course, not limited thereto.

[0073] [Chemical 9] 1

As other raw materials, a fluorine compound can be used, and as the organic fluorine compound, a fluorocarbon gas, a fluorinated hydrocarbon gas, or the like can be preferably used. Examples of the fluorocarbon gas include tetrafluoromethane, tetrafluoroethylene, hexafluoropropylene, octafluorocyclobutane, and the like. Examples of the fluorinated hydrocarbon gas include difluoromethane, tetrafluoroethane, tetrafluoropropylene, trifluoropropylene, and the like. In addition, for example, halogenated fluoride compounds such as black trifluoromethane, chlorodifluoromethane, dichlorotetrafluorocyclobutane, fluoroalcohols such as trifluoromethanol and pentafluoroethanol, trifluoroacetic acid, etc. , Fluorinated fats such as pentafluoropropionic acid The ability to use organic fluorine compounds such as fluorinated ketones such as fatty acid and hexafluoroacetone is not limited to these. Further, these compounds may have a fluorinated ethylene unsaturated group in the molecule.

[0075] The silane compound having an alkyl group and the silane compound having an aromatic group according to the present invention can be mixed and used at a mass ratio of 1:99 to 99: 1, and a mass of 10:90 to 90:10. More preferably, the ratio is 20:80 to 80:20.

[0076] The surface treatment layer according to the present invention is formed on a substrate described later, and an organic semiconductor layer is further formed thereon. The thickness of the surface treatment layer is preferably lOOnm or less from the monomolecular layer, and more preferably lOnm or less from the monomolecular layer.

[0077] The surface roughness Ra of the surface treatment layer surface is greatly affected by the surface properties of the substrate, the gate electrode, and the gate insulating film when the thin film transistor is a bottom gate type described later. 01-: Ability to be LOnm A viewpoint power of carrier mobility of transistor elements is also preferable

[Pretreatment method, surface treatment layer forming method]

The method for forming the surface treatment layer is not particularly limited, but vacuum deposition, molecular beam epitaxy, ion cluster beam, low energy ion beam, ion plating, CVD, sputtering, atmospheric pressure plasma ( Atmospheric pressure plasma (CV D method), dip coating method, casting method, reel coating method, bar coating method, die coating method, etc., and wet processes such as printing and ink jet patterning methods. Can be used according to.

[0079] Among them, as a method preferably used in the present invention, a wet method in which a substrate is immersed in a solution of a surface treatment agent or a solution of a surface treatment agent is applied and dried, a plasma CVD method, preferably an atmospheric pressure plasma CVD method is used. Can be mentioned.

[0080] (Wet method)

In the wet method, for example, the substrate is dipped in a 1% by weight toluene solution of a surface treatment agent for 10 minutes and then dried, or this solution is applied to the substrate and dried.

[0081] (Plasma CVD method, atmospheric pressure plasma CVD method)

Surface treatment agent (in plasma CVD method, surface treatment layer forming material is the raw material) A reactive gas is supplied onto a substrate heated in the range of 50 to 500 ° C and a surface treatment layer is formed by a thermal reaction. Using 0.01, the effect of the present invention can be obtained even when using a general plasma CVD method performed under a reduced pressure of LOOPa, but the mobility is improved and the surface treatment layer is uniform. The atmospheric pressure plasma method is most preferable from the viewpoints of the performance, the formation speed of the surface treatment layer, and the efficient production in a non-vacuum system.

The atmospheric pressure plasma method that can be preferably applied to the present invention will be described in detail below.

FIG. 1 is a conceptual diagram showing an example of a plasma discharge treatment container 20 used in the plasma discharge treatment apparatus P. In a slightly different embodiment, the plasma discharge treatment container 20 shown in FIG. 2 is used.

In FIG. 1, a long film-like substrate F is conveyed while being wound around a portal electrode 21 that rotates in the conveying direction (clockwise in the figure). The fixed electrode 22 is composed of a plurality of cylinders, and is installed facing the roll electrode 21. The substrate F wound around the roll electrode 21 is pressed by the two-up rollers 23a and 23b, is regulated by the guide roller 24, is transported to the discharge treatment space secured by the plasma discharge treatment vessel 20, is subjected to discharge plasma treatment, Then, it is conveyed to the next process via the guide roller 25. Further, the partition plate 26 is disposed in the vicinity of the above-mentioned roller 23b, and suppresses the air accompanying the base F from entering the plasma discharge processing container 20.

This entrained air can be achieved by the above-mentioned roller 23b, which is preferably suppressed to 1% by volume or less with respect to the total gas volume in the plasma discharge treatment vessel 20. is there.

[0086] Note that a mixed gas (discharge gas and reaction gas; the surface treatment agent is included in the reaction gas) used for the discharge plasma treatment is introduced into the plasma discharge treatment vessel 20 from the air supply port 27, and after the treatment, The gas is exhausted from the exhaust port 28.

FIG. 2 is a schematic view showing another example of the plasma discharge treatment container 20 as described above, whereas the plasma discharge treatment container 20 of FIG. 1 uses a cylindrical fixed electrode 22. In the plasma discharge treatment container 20 shown in FIG. 2, a prismatic fixed electrode 29 is used. Compared with the cylindrical fixed electrode 22 shown in FIG. 1, the prismatic fixed electrode 29 shown in FIG. 2 is preferably used in the production method of the present invention.

FIGS. 3A and 3B are schematic perspective views showing an example of the cylindrical roll electrode 21 described above, and FIG.

FIGS. 5A and 5B are schematic perspective views showing an example of a cylindrical fixed electrode 22, and FIGS. 5A and 5B are schematic perspective views showing an example of a prismatic fixed electrode 29. FIG.

In FIG. 3 (a), a roll electrode 21 serving as a ground electrode is formed by applying a ceramic-coated dielectric 21b that has been subjected to sealing treatment using an inorganic material after thermal spraying ceramics on a conductive base material 21a such as metal. It consists of a combination of coatings. Ceramic coated dielectric material 21b is covered with lmm with a single wall, manufactured to have a roll diameter of 200mm after coating, and grounded.

Further, as shown in FIG. 3 (b), a roll electrode 21 is formed by a combination of a ceramic-coated dielectric 21B provided with an inorganic material by a conductive base material 21A, such as a metal, and a covering. Also good. As the lining material, silicate glass, borate glass, phosphate glass, germanate glass, tellurite glass, aluminate glass, vanadate glass, etc. are preferably used. Among these, borate glass is more preferable because it is easy to process. As the conductive base materials 21a and 21A such as metal, stainless steel or titanium is preferable from the viewpoint of force processing including metals such as titanium, silver, platinum, stainless steel, aluminum and iron. As a ceramic material used for thermal spraying, alumina, silicon nitride, or the like is preferably used. Among these, alumina is more preferable because it is easy to process.

In this embodiment, the conductive base materials 21a and 21A of the roll electrode are made of a stainless steel jacket roll base material having a constant temperature means using liquid (not shown).

[0093] FIGS. 4 (a), (b) and FIGS. 5 (a), (b) have a fixed electrode 22 and a fixed electrode 29 as application electrodes, and are in the same combination as the roll electrode 21 described above. It is configured.

[0094] The power source for applying voltage to the applied electrode is not particularly limited, but Shinko Electric's high frequency power supply (50 kHz), Heiden Laboratory high frequency power supply (continuous mode use, 100 kHz), Pul Kogyo high frequency power supply ( 200kHz), Pearl Industrial High Frequency Power Supply (800kHz), Pearl High Industrial Power Supply (2MHz), JEOL High Frequency Power Supply (13. 56MHz), Pearl Industrial A high-frequency power source (27 MHz), a high-frequency power source (150 MHz) manufactured by Pearl Industry, etc. can be preferably used. A power source that oscillates at 433 MHz, 800 MHz, 1.3 GHz, 1.5 GHz, 1.9 GHz, 2.45 GHz, 5.2 GHz, or 10 GHz may be used.

FIG. 6 is a conceptual diagram showing an example of a plasma discharge treatment apparatus P used in the present invention.

In FIG. 6, the portion of the plasma discharge processing vessel 20 has the same force as described in FIG. 2, and further includes a gas generator 40, a power source 50, an electrode constant temperature unit 70, and the like as a device configuration. As a thermostat for the electrode thermostat unit 70, an insulating material such as distilled water or oil is used.

The electrodes shown in FIG. 6 are the same as those shown in FIGS. 3 and 5, and the gap between the opposing electrodes is set to about 1 mm, for example.

The distance between the electrodes is determined in consideration of the thickness of the solid dielectric placed on the electrode base material, the magnitude of the applied voltage, the purpose of using plasma, and the like. The shortest distance between the solid dielectric and the electrode when a solid dielectric is placed on one of the electrodes, and the shortest distance between the solid dielectrics when a solid dielectric is placed on both of the electrodes are uniform in any case From the viewpoint of effective discharge, 0.5 to 20 mm is preferable, and 1 ± 0.5 mm is particularly preferable.

[0099] A roll electrode 21 and a fixed electrode 29 are arranged at predetermined positions in the plasma discharge treatment vessel 20, the flow rate of the mixed gas generated by the gas generator 40 is controlled, and air is supplied via the gas filling means 41. The plasma discharge treatment vessel 20 is put into the plasma discharge treatment vessel 20 through the port 27, and the inside of the plasma discharge treatment vessel 20 is filled with the mixed gas used for the plasma treatment and exhausted through the exhaust port 28. Next, a voltage is applied to the electrode by the power source 50, and the roll electrode 21 is grounded to the ground, and discharge plasma is generated. Here, the substrate F is supplied from the roll-shaped original winding substrate 60, and the electrodes in the plasma discharge treatment vessel 20 are in a single-sided contact state (in contact with the roll electrode 21) via the guide roller 24. Be transported. Then, the surface of the substrate F is formed by discharge plasma during conveyance, and after the surface treatment layer containing the inorganic substance derived from the reactive gas (including the surface treatment agent) in the mixed gas is formed on the surface, the guide roller It is conveyed to the next process via 25. Here, the substrate F is in contact with the roll electrode 21, and only the surface is formed.

[0100] The value of the voltage applied from the power supply 50 to the fixed electrode 29 is determined appropriately. For example, the voltage is about 0.5 to: LOkV, and the power supply frequency is adjusted to more than 1kHz and less than 150MHz. Here, regarding the power supply method, either a continuous sine wave continuous oscillation mode called continuous mode or an intermittent oscillation mode called ON / OFF intermittently called pulse mode may be adopted.

[0101] As for the discharge power, depends force preferably by the shape of the device discharge density of 0. 1~5 OZcm ² is Yo,.

[0102] Next, an atmospheric pressure plasma discharge method and apparatus for applying a high frequency voltage of two frequencies will be described. The discharge condition with the two high-frequency voltages is that a high-frequency voltage is applied to the discharge space formed by the opposing electrodes (referred to here as the first electrode and the second electrode), and the high-frequency voltage is the first frequency. Voltage component of ω and second frequency ω higher than the first frequency ω

It has at least a component superposed on the voltage component of 1 1 2.

[0103] A high frequency means a frequency having a frequency of at least 0.5 kHz.

[0104] The high frequency voltage is higher than the voltage component of the first frequency ω and the first frequency ω.

1 1 The component with the voltage component of the second frequency ω superimposed, and its waveform is

2 1 A sine wave with a higher frequency ω is superimposed on the sine wave.

twenty one

It has a jagged waveform.

[0105] In the present invention, the lowest voltage that can cause discharge in the discharge space (electrode configuration, etc.) and reaction conditions (gas conditions, etc.) used in the actual surface treatment layer forming method. Is called the discharge start voltage. The discharge start voltage varies somewhat depending on the type of gas supplied to the discharge space, the dielectric type of the electrode, etc., but may be considered to be substantially the same as the discharge start voltage of the discharge gas alone.

[0106] By applying a high-frequency voltage as described above between the opposing electrodes (discharge space), a discharge capable of forming a surface treatment layer is generated, and high-density plasma necessary for forming a high-quality surface treatment layer is generated. It is estimated that you can. What is important here is that such a high-frequency voltage is applied to each of the opposing electrodes, that is, it is applied from both to the same discharge space. The surface treatment layer formation of the present invention cannot be achieved by a method in which two application electrodes are juxtaposed and a high-frequency voltage of a different frequency is applied to each of the spaced apart discharge spaces.

[0107] The force described above for the superposition of sine waves is not limited to this. Even if it is a Rus wave, it does not work even if one is a sine wave and the other is a pulse wave. Also

Further, it may have a third voltage component.

[0108] As a specific method of applying the above-described high-frequency voltage between the counter electrodes (same discharge space), the first high-frequency voltage V is applied to the first electrode constituting the counter electrode.

1 1

Connect the first power supply that applies the voltage, and connect the second electrode with the frequency ω and the voltage V to the second electrode.

This is an atmospheric pressure plasma discharge treatment apparatus connected to a second power source for applying a high frequency voltage of 2 2.

[0109] The atmospheric pressure plasma discharge treatment apparatus includes gas supply means for supplying a discharge gas and a surface treatment layer forming gas between the counter electrodes. Furthermore, it is preferable to have an electrode temperature control means for controlling the temperature of the electrode.

[0110] Also, it is preferable to connect a first filter between the electrode and the first power source or between them, and connect a second filter between the electrode and the second power source or between them. The first filter 1 makes it difficult for current at the frequency of the first power supply to pass through, and more easily passes current at the frequency from the second power supply. Use a filter that has a function for each filter that makes it difficult to pass a current with a frequency of two power supplies and makes it easier to pass a current with a frequency of the first power supply. Here, being difficult to pass means that it preferably passes only 20% or less, more preferably 10% or less of the current. On the contrary, the phrase “easy to pass” means that 80% or more, more preferably 90% or more of the current is passed.

[0111] Furthermore, it is preferable that the first power source of the atmospheric pressure plasma discharge treatment apparatus has a capability of applying a higher frequency voltage than the second power source.

[0112] As another discharge condition in the present invention, a high-frequency voltage is applied between the first electrode and the second electrode facing each other, and the high-frequency voltage is applied to the first high-frequency voltage V and the second high-frequency voltage. High frequency

1

When the voltage V is superimposed and the discharge start voltage is IV,

2

V≥IV> V

1 2

Or V> IV≥V. More preferably,

1 2

V> IV> V is satisfied.

1 2

[0113] The definition of the high frequency and the discharge start voltage, and the specific method for applying the high frequency voltage of the present invention between the counter electrodes (same discharge space) are the same as those described above. [0114] Here, the high-frequency voltage (applied voltage) and the discharge start voltage are those measured by the following methods.

[0115] Measuring method of high frequency voltage V and V (unit: kV / mm):

1 2

Install a high-frequency probe (P6015A) for each electrode, connect the high-frequency probe to an oscilloscope (Tektronix, TDS3012B), and measure the voltage.

[0116] Measurement method of discharge start voltage IV (unit: kV / mm):

The discharge gas is supplied between the electrodes, the voltage between the electrodes is increased, and the voltage at which discharge starts is defined as the discharge start voltage IV. The measuring instrument is the same as the above high-frequency voltage measurement.

[0117] By adopting a discharge condition that applies a high voltage, even a discharge gas with a high discharge start voltage, such as nitrogen gas, can start the discharge gas and maintain a high-density and stable plasma state. Surface treatment layer formation can be performed.

[0118] When the discharge gas is nitrogen gas according to the above measurement, the discharge start voltage IV is 3.7 kV.

Therefore, in the above relationship, the first high-frequency voltage is V≥3.7k

1

By applying it as VZmm, the nitrogen gas can be excited and put into a plasma state.

Here, the frequency of the first power supply is preferably 200 kHz or less. The electric field waveform may be a sine wave or a nors wave. The lower limit is preferably about 1kHz.

[0120] On the other hand, the frequency of the second power source is preferably 800 kHz or more. The higher the frequency of the second power source, the higher the plasma density, and a dense and high-quality surface treatment layer can be obtained. The upper limit is preferably about 200MHz.

[0121] The application of a high-frequency voltage from such two power sources depends on the first frequency ω side.

1 is necessary to start discharge of a discharge gas having a high discharge start voltage, and the second frequency ω side is used to increase the plasma density to form a dense and high-quality surface treatment layer.

2

This is an important point of the present invention.

[0122] In the present invention, the first filter makes it difficult for a current having a frequency from the first power source to pass through and allows a current having a frequency of the second power source to easily pass. In addition, the second filter is difficult to pass a current having a frequency from the second power source. This makes it easier to pass the current of the frequency from the first power source. In the present invention, any filter having such properties can be used without limitation.

[0123] For example, as the first filter, a capacitor of several tens to several tens of thousands of pF or a coil of about several H can be used depending on the frequency of the second power supply. The second filter can be used as a filter by using a coil of 10 H or more according to the frequency of the first power source and grounding it through these coils or capacitors.

[0124] The first power supply and the second power supply may not be necessarily used at the same time, but may be used alone. In this case, the same effect as when a single high frequency power supply is applied is obtained.

[0125] As described above, the atmospheric pressure plasma discharge treatment apparatus discharges between the counter electrodes, and at least the discharge gas and the surface treatment layer forming gas (reaction gas) introduced between the counter electrodes are in a plasma state. In the case where the substrate is placed between the counter electrodes, the surface treatment layer is formed on the substrate by exposing the substrate to be transported to the plasma state gas (see, for example, FIGS. 1 to 7). ). As another method, the atmospheric pressure plasma discharge treatment apparatus discharges between the counter electrodes similar to the above, excites the gas introduced between the counter electrodes, or puts it in a plasma state, and jets the gas outside the counter electrode. A surface treatment layer is formed on the substrate by blowing a gas in an excited or plasma state to the substrate and exposing the substrate in the vicinity of the counter electrode (stationary or transported). There is a jet-type device that forms water (see Figure 8 below)

[0126] As another method, as shown in Fig. 9 to be described later, the discharge gas G is introduced into the discharge spaces formed by the two pairs of counter electrodes 211-221, 212-222, respectively, and excited. The surface treatment layer is formed on the substrate F by contacting or mixing the discharge gas G ′ and the surface treatment layer forming gas (reaction gas) M containing the raw material for the surface treatment layer outside the discharge space. You can also. Reference numeral 213 denotes an insulating layer.

[0127] The plasma discharge treatment vessel 20 is preferably made of an insulating material such as a Pyrex (registered trademark) glass treatment vessel, but may be made of metal as long as it can be insulated from the electrodes. For example, polyimide resin or the like may be attached to the inner surface of an aluminum or stainless steel frame, and ceramic spraying may be performed on the metal frame to achieve insulation. [0128] In order to minimize the influence on the substrate during the discharge plasma treatment, the temperature of the substrate during the discharge plasma treatment is adjusted to a temperature between room temperature (15-25 ° C) and less than 300 ° C. It is preferable to adjust to room temperature to 200 ° C. However, these conditions are not limited to this range because the upper limit of the temperature is determined depending on the physical properties of the substrate, particularly the glass transition temperature. In order to adjust to the above temperature range, the electrode and the substrate are subjected to discharge plasma treatment while being cooled by a cooling means as necessary.

[0129] In the embodiment of the present invention, the plasma treatment is preferably performed at atmospheric pressure or near atmospheric pressure, but the plasma treatment may be performed under vacuum or high pressure. The vicinity of atmospheric pressure represents a pressure of 20 to L lOkPa, but 93 to 104 kPa is preferable in order to obtain the effect described in the present invention.

[0130] In addition, in an electrode for discharge used for atmospheric pressure plasma treatment, the surface of at least the surface in contact with the substrate F has a maximum surface roughness (Rmax) specified by JIS B 0601 of 10 m. It is preferable that the surface roughness is adjusted so as to be equal to or less than the maximum value of the surface roughness.

[0131] Note that the plasma discharge treatment apparatus P shown in FIGS. 1 and 2 described above is a force used when the substrate F is a film. For example, a substrate having a thickness greater than the film, for example, If it is a lens or the like, a plasma discharge treatment apparatus P as shown in FIG. 7 is used. FIG. 7 is a schematic view showing another example of the plasma discharge treatment apparatus P.

In this plasma discharge processing apparatus P, a plate-type electrode 103 is used as an electrode connected to the high-frequency power supply 101, and a base (for example, a lens L) is placed on the electrode 103.

On the other hand, as an electrode connected to the low-frequency power source 102, a rectangular bar-shaped electrode 104b is provided so as to face the electrode 103. The square rod-shaped electrode 104a is grounded as a ground. In this case, the mixed gas is supplied from above the electrodes 104 a and 104 b, and a plasma state is obtained in a range where the force between the electrodes 104 a and 104 b extends over the electrode 103.

FIG. 8 is a schematic view showing another example of an atmospheric pressure plasma discharge apparatus useful for the present invention.

The plasma discharge treatment apparatus P has a counter electrode composed of a first electrode 111 and a second electrode 112, and the first electrode 111 is connected to the first power supply 121 between the counter electrodes. First A high-frequency voltage V of frequency ω is applied, and the second electrode 112 is connected to the second power source 122.

1 1

The high frequency voltage V of the second frequency ω is applied. First power supply 121

twenty two

It has the ability to apply a higher frequency voltage (V> V) than the second power supply 122, and

1 2

1 The first frequency ω of the power supply 121 is lower than the second frequency ω of the second power supply 122.

1 2

It ’s a caro.

A first filter 123 is installed between the first electrode 111 and the first power supply 121 so that the current from the first power supply 121 flows toward the first electrode 111. It is designed to make it difficult to pass current from the second power source 122 and to pass current from the second power source 122 more easily.

[0137] Further, the second filter 124 is installed between the second electrode 112 and the second power source 122 so that the current from the second power source 122 flows toward the second electrode 112. It is designed to pass the current from the two power sources 122 and to easily pass the current from the first power source 121.

[0138] Gas G is introduced from the gas supply means 113 between the opposing electrodes of the first electrode 111 and the second electrode 112 (discharge space), and a high-frequency voltage is applied from the first electrode 111 and the second electrode 112. A discharge is generated, and while the gas G is in a plasma state, the gas G is blown out in the form of a jet to the lower side of the counter electrode (the lower side of the paper) to create a plasma G Then, a surface treatment layer is formed on the substrate F in the vicinity of the treatment position 114.

FIG. 9 is a schematic diagram showing still another example of an atmospheric pressure plasma discharge treatment apparatus useful for the present invention.

[0140] The atmospheric pressure plasma discharge treatment apparatus of Fig. 9 mainly includes a counter electrode in which the first electrode 211 and the second electrode 221 and the first electrode 212 and the second electrode 222 are arranged to face each other. In addition to the high-frequency power supply 50 that applies a high-frequency electric field between the counter electrodes, which are voltage application means, the discharge gas G is placed in the discharge space, and the reaction (surface treatment layer formation) gas M is placed outside the discharge space. It comprises gas supply means to be introduced, electrode temperature adjusting means for controlling the electrode temperature, and the like.

[0141] A region having a dielectric 213 sandwiched between the first electrode 211 and the second electrode 221 or between the first electrode 212 and the second electrode 222 and having a strong diagonal line on the first electrode is a discharge space. . This discharge The discharge gas G is introduced into the space and excited. Further, no discharge occurs in the region sandwiched between the second electrodes 221 and 22, and the surface treatment layer forming gas M is introduced here. Next, in the region outside the discharge space where no counter electrode exists, the excited discharge gas G ′ and the surface treatment layer forming gas M are brought into contact with each other as an indirect excitation gas. Expose to form a surface treatment layer.

[0142] Here, it is illustrated that a single-frequency high-frequency voltage is applied, but a high-frequency electric field of two frequencies may be applied using the method described above.

The gas used varies depending on the type of surface treatment layer to be provided on the substrate. Basically, it is a mixed gas of discharge gas (inert gas) and reaction gas containing surface treatment agent for forming the surface treatment layer. is there. The reaction gas is preferably contained in an amount of 0.01 to LO volume% with respect to the mixed gas. The content is more preferably 0.1 to 10% by volume, and still more preferably 0.1 to 5% by volume.

[0144] Examples of the inert gas include Group 18 elements in the periodic table, specifically, helium, neon, argon, krypton, xenon, radon, nitrogen gas, and the like. In order to obtain it, helium, argon, or nitrogen gas is preferably used.

[0145] Further, the reaction is controlled by containing 0.01 to 5% by volume of a component selected from oxygen, ozone, hydrogen peroxide, carbon dioxide, carbon monoxide, hydrogen, and nitrogen in the mixed gas, A good surface treatment layer can be formed.

[0146] Further, in order to introduce the surface treatment agent of the reactive gas between the electrodes which are the discharge spaces, it may be in any state of gas, liquid or solid at normal temperature and pressure. In the case of gas, it can be introduced into the discharge space as it is, but in the case of liquid or solid, it is used after being vaporized by means such as heating, decompression or ultrasonic irradiation.

[0147] An organic thin film transistor has a source electrode and a drain electrode connected to each other by an organic semiconductor channel (active layer, organic semiconductor layer) on a base, and a top gate type having a gate electrode on the gate electrode via a gate insulating layer. (Fig. 10 (a) to (c)) and a bottom gate type having a gate electrode on a substrate and a source electrode and a drain electrode connected by an organic semiconductor channel through a gate insulating layer ( Figure 10 (c!) To (f)). The organic thin film transistor of the present invention is Although these top gate type and bottom gate type may be shifted, an organic thin film transistor having a bottom gate type structure, particularly an organic thin film transistor having a bottom gate type structure shown in FIG.

[0148] Next, components of the organic thin film transistor constituting the present invention will be described.

[Organic semiconductor layer]

(Organic semiconductor materials)

As the organic semiconductor material constituting the organic semiconductor layer, various condensed polycyclic aromatic compounds and conjugated compounds can be applied.

[0150] The organic semiconductor material preferably has an alkyl group in view of solubility and affinity with the thin film formed by the pretreatment agent. The alkyl group has 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms.

[0151] Examples of the condensed polycyclic aromatic compound include anthracene, tetracene, pentacene, hexacene, heptacene, taricene, picene, fluorene, pyrene, peropyrene, perylene, terylene, ku-terylene, coronene, tal-no-lene. In addition, compounds such as musantracene, bisanthene, bisanthene, heptazethrene, pyranslen, violanthene, isoviolanthene, cercobiphenyl, phthalocyanine, porphyrin, and derivatives thereof are listed.

[0152] Examples of the conjugated compound include polythiophene and its oligomer, polypyrrole and its oligomer, polyaniline, polyphenylene and its oligomer, polyphenylene vinylene and its oligomer, polyphenylene vinylene and its oligomer, polyacetylene, Examples include polydiacetylenes, tetrathiafulvalene compounds, quinone compounds, cyan compounds such as tetracyanoquinodimethane, fullerenes, and derivatives or mixtures thereof.

[0153] Further, among polythiophene and oligomers thereof, thiophene hexamer, α-secthiophene e, ω-dihexinore a-secciothiophene, e, ω-dihexinore a-quinketiophene, α, ω Oligomers such as —bis (3-butoxypropyl) -a-secciothiophene can be preferably used.

Further, copper phthalocyanine is a metal phthalocyanine such as fluorine-substituted copper phthalocyanine described in JP-A-11-251601, naphthalene 1, 4, 5, 8-tetracarboxylic acid diimide, N, N 'bis (4 trifluoromethylbenzyl) naphthalene 1, 4, 5, 8-tetracarboxylic acid diimide, N, N' -bis (1H, 1H-perfluorooctyl), N, N '-bis (1H, 1H-perfluorobutyl) and N, N '-dioctylnaphthalene 1, 4, 5, 8- tetracarboxylic diimide derivatives, naphthalene 2, 3, 6, 7 naphthalene such as tetracarboxylic diimide Tetracarboxylic acid diimides, and condensed ring tetracarboxylic acid diimides such as anthracene tetracarboxylic acid diimides such as anthracene 2, 3, 6, 7-tetracarboxylic acid diimide, C, C, C, C, C, etc. fullerene Carbon nanotubes such as SWNT

60 70 76 78 84

And pigments such as merocyanine pigments and hemicyanine pigments.

[0155] Among these π-conjugated materials, at least one selected from the group consisting of condensed polycyclic aromatic compounds such as pentacene, fullerenes, condensed ring tetracarboxylic acid diimides, and metal phthalocyanines is included. Favored ,.

[0156] Other organic semiconductor materials include tetrathiafulvalene (TTF) -tetracyanoquinodimethane (TCNQ) complex, bisethylenetetrathiafulvalene (BEDTTTF) -perchloric acid complex, BEDTTTF iodine complex, TCNQ iodine complex, etc. Organic molecular complexes of can also be used. Furthermore, σ conjugated polymers such as polysilane and polygermane can also be used organic / inorganic hybrid materials described in JP-A-2000-260999.

[0157] Of the polythiophene and oligomers thereof, a thiophene oligomer represented by the following general formula (9) is preferred.

[0158] [Chemical 10]

-General formula (9>

[0159] In the formula, R represents a substituent.

[0160] Thiophene oligomer represented by the general formula (9)

The thiophene oligomer represented by the general formula (9) will be described.

[0161] In the general formula (9), examples of the substituent represented by R include an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert butyl group, a pentyl group, Xyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (eg, bur group, allyl group, etc.) , Alkyl groups (eg, ethynyl group, propargyl group, etc.), aryl groups (eg, phenol group, p-chlorophenol group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group) Group, azulenyl group, acenaphthyl group, fluorenyl group, phenanthryl group, indur group, pyrenyl group, biphenyl group, etc.), aromatic heterocyclic group (for example, furyl group, chenyl group, pyridyl group, pyridazyl group, pyrimidyl group) , Virazyl group, triazyl group, imidazolyl group, pyrazolyl group, thiazolyl group, benzimidazolyl group, benzoxazolyl Group, quinazolyl group, phthalazyl group, etc.), heterocyclic group (eg, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxyl group (eg, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group) Group, octyloxy group, dodecyloxy group, etc.), cycloalkoxyl group (eg, cyclopentyloxy group, cyclohexyloxy group, etc.), aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), alkylthio group (eg, methylthio group, Ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio group (eg, cyclopentylthio group, cyclohexylthio group, etc.), arylthio group (eg, phenylthio group) Group Tilthio group, etc.), alkoxy carboxylic groups (eg methyloxy carbo yl group, eth oxy carboxy group, butyl oxy carbo ol group, octyl oxy carbo ol group, dodecyl oxy group) -Aryl group, etc.), arylcarbonyl group (for example, phenylcarbol group, naphthyloxycarbonyl group, etc.), sulfamoyl group (for example, aminosulfol group, methylaminosulfol group) Dimethylaminosulfol group, butylaminosulfol group, hexylaminosulfol group, cyclohexylaminosulfol group, octylaminosulfol group, dodecylaminosulfol group, phenol Ruaminosulfol group, naphthylaminosulfol group, 2-pyridylaminosulfol group, etc.), acyl group (for example, acetyl group, ethylcarbol group, propylcarbol group) , Pentyl carbo yl group, cyclohexyl carbonyl group, octyl carbo ol group, 2-ethyl hexyl carbo ol group, dodecyl carbonyl group, chloro carbonyl group, naphthyl carbo ol group, pyridyl carbo ol Group), isyloxy group (for example, acetyloxy group, ethyl carbo-loxy group, butyl carbo-loxy group, octyl carbo-loxy group, dodecyl carbo-loxy group, phenylcarbonyl group, etc.), amide group (for example, Methylcarbonylamino group, ethyl carbolumino group, dimethyl carbolumino group, propyl carbolumino group, pentyl carbolumino group, cyclohexyl carbolumino group, 2-ethyl hexylcarbo-lamino group, octylcarbo-lumino group, Dodecyl carbolumino group, phenol carbolumino group, naphthyl carbolumino group, etc., strong rubamoyl group (eg, amino carbo yl group, methyl amino carbo ol group, dimethyl amino carbo ol group, propyl Aminocarbol group, pentylaminocarbol group, Roxylaminocarbol group, Octylaminocarboxyl group, 2-Ethylhexylaminocarbol group, Dodecylaminocarbol group, Phenylaminocarbol group, Naphtylaminocarbol- Group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido group) , 2-pyridylaminoureido group, etc.), sulfier groups (for example, methyl sulfyl group, ethyl sulfyl group, propyl sulfyl group, cyclohexyl sulfiel group, 2-ethyl hexyl sulfiel group, dodecyl sulfier group) , Phenylsulfuryl group, naphthylsulfuric group, 2-pyridylsulfuric group- Group), alkylsulfol group (for example, methylsulfol group, ethylsulfol group, butylsulfol group, cyclohexylsulfol group, 2-ethylhexylsulfol group, dodecylsulfol group, etc.) ), Arylsulfol groups (for example, phenylsulfol group, naphthylsulfol group, 2-pyridylsulfol group, etc.), amino groups (for example, amino group, ethylamino group, dimethylamino group, ptylamino group, cyclopentyl group) Tyramino group, 2-ethylhexylamino group, dodecylamino group, arlino group, naphthylamino group, 2-pyridylamino group, etc., halogen atom (eg fluorine atom, chlorine atom, bromine atom etc.), fluorinated hydrocarbon group (For example, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, pentafluorophenyl group, etc.), cyan group And silyl groups (for example, trimethylsilyl group, triisopropylpropylsilyl group, triphenylsilyl group, ferroethylsilyl group, etc.). [0162] These substituents may be further substituted with the above substituents, or a plurality thereof may be bonded to each other to form a ring.

[0163] Among them, a preferable substituent is an alkyl group, more preferably an alkyl group having 2 to 20 carbon atoms, and particularly preferably an alkyl group having 6 to 12 carbon atoms.

[0164] <End group of thiophene oligomer>

The terminal group of the thiophene oligomer used in the present invention will be described.

[0165] It is preferable that the terminal group of the thiophene oligomer used in the present invention does not have a chael group. Further, as the preferable group as the terminal group, an aryl group (for example, a phenyl group, p-Chlorofuryl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulyl group, acenaphthyl group, fluoro group, phenanthryl group, indenyl group, pyrenyl group, biphenyl group Etc.), alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, etc.) And halogen atoms (for example, fluorine atom, chlorine atom, bromine atom, etc.).

[0166] <Conformational characteristics of repeating unit of thiophene oligomer>

The thiophene oligomer used in the present invention preferably has no head-to-head structure in the structure, more preferably, the structure has a head-to-tail structure, or It preferably has a tail-to-tail structure.

[0167] Regarding the Head-to-Head structure, Head-to-Tail structure, and Tail-to-Tail structure according to the present invention, for example, "π-electron organic solid" (1998, published by the Japan Society for Publishing Press, Japan) This can be referred to from pages 27 to 32, Adv. Mater. 1998, 10, No. 2, pages 93 to 116, etc. Here, specific structural features are shown below.

[0168] Here, R has the same meaning as R in the general formula (9).

[0169] [Chemical 11] Head—to—Head structure

[0170] [Chemical 12]

Head— to— Tail structure

[0171] [Chemical 13]

Tail—to-Tail structure

[0172] Hereinafter, the ability to show specific examples of these thiophene oligomers used in the present invention is not limited thereto.

[0173] [Chemical 14]

[0174] [Chemical 15]

[0175] [Chemical 16]

[0176] [Chemical 17]

[0177] A method for producing these thiophene oligomers is described in Japanese Patent Application No. 2004-172317 (June 2004, 10th appearance) by the present inventors.

[0178] In the present invention, the organic semiconductor layer may be formed of a material having a functional group such as acrylic acid, acetamide, a dimethylamino group, a cyano group, a carboxyl group, or a nitro group, a benzoquinone derivative, or a tetracyano. Ethylene and tetracyanoquinodimethane and their derivatives For example, a material that serves as an acceptor for accepting electrons, such as a material having a functional group such as an amino group, a triphenyl group, an alkyl group, a hydroxyl group, an alkoxy group, or a full group, or a substituted amine such as phenylenediamine. , Anthracene, benzoanthracene, substituted benzoanthracene, pyrene, substituted pyrene, force rubazole and its derivatives, tetrathiafulvalene and its derivatives, etc. You can do so.

[0179] The doping means introducing an electron-donating molecule (acceptor) or an electron-donating molecule (donor) into the thin film as a dopant. Therefore, the doped thin film is a thin film containing the condensed polycyclic aromatic compound and the dopant. A well-known thing can be employ | adopted as a dopant used for this invention.

[0180] As a method for forming these organic semiconductor layers, they can be formed by a known method, for example, vacuum deposition, MBE (Molecular Beam Epitaxy), ion cluster beam method, low energy ion beam method, ion plate. Coating method, sputtering method, CVD (Chemical Vapor Deposition), laser deposition, electron beam deposition, electrodeposition, spin coating, dip coating, bar coating method, die coating method, spray coating method, LB method, etc., screen printing, Examples thereof include ink jet printing and blade coating.

[0181] Among these, in terms of productivity, solution process methods that can easily and precisely form thin films using organic semiconductor solutions, such as spin coating, blade coating, dip coating, roll coating, bar coating, A coating method, a die coating method or the like is preferred.

[0182] As described in Advanced Material 1999 No. 6, p480-483, if the precursor such as pentacene is soluble in the solvent, the precursor film formed by coating is heat-treated. A thin film of the target organic semiconductor material may be formed.

[0183] The film thickness of these organic semiconductor layers is not particularly limited, but the characteristics of the obtained transistor are largely influenced by the film thickness of the organic semiconductor layer. Different forces depending on the conductor Generally 1 _μm or less, particularly 10 to 300 nm is preferred.

[0184] (Electrode)

In the organic thin film transistor of the present invention, the source or drain electrode material is not particularly limited as long as it is a conductive material, and is formed of a known electrode material. As electrode material There is no particular limitation as long as it is a conductive material, and platinum, gold, silver, nickel, chromium, copper, iron, tin, antimony lead, tantalum, indium, palladium, tellurium, rhenium, iridium, aluminum, Ruthenium, germanium, molybdenum, tungsten, tin oxide 'antimony, indium oxide' tin (ITO), fluorine doped zinc oxide, zinc, carbon, graphite, glassy carbon, silver paste and carbon paste, lithium, beryllium , Sodium, magnesium, potassium, calcium, scandium, titanium, manganese, zirconium, gallium, niobium, sodium, sodium monopotassium alloy, magnesium, lithium, aluminum, magnesium Z copper mixture, magnesium Z silver mixture, magnesium Z aluminum Mixture, Magnesium Z indium mixture, aluminum Z oxide-aluminum mixture, lithium Z aluminum mixture, etc. are used. Alternatively, a known conductive polymer whose conductivity has been improved by doping, such as conductive polyarlin, conductive polypyrrole, or conductive polythiophene (polyethylenedioxythiophene and polystyrenesulfonic acid complex, etc.) is also preferably used. It is done.

[0185] Among the materials listed above, materials having low electrical resistance at the contact surface with the semiconductor layer are preferred as materials for forming the source electrode or drain electrode. Particularly in the case of a P-type semiconductor, white gold, gold, silver , Ιτο, conductive polymers and carbon are preferred.

[0186] When the source electrode or the drain electrode is used, it is formed using a fluid electrode material such as a solution, paste, ink, or dispersion liquid containing the above conductive material, in particular, a conductive polymer, Alternatively, a fluid electrode material containing fine metal particles containing platinum, gold, silver and copper is preferred. The solvent or dispersion medium is preferably a solvent or dispersion medium containing 60% or more, preferably 90% or more of water, in order to suppress damage to the organic semiconductor.

[0187] As the fluid electrode material containing fine metal particles, for example, a known conductive paste or the like may be used. Preferably, fine metal particles having a particle diameter of 1 to 50 nm, preferably 1 to: LOnm are used. A material dispersed in water or a dispersion medium that is an arbitrary organic solvent using a dispersion stabilizer as required.

[0188] The material of the metal fine particles is platinum, gold, silver, nickel, chromium, copper, iron, tin, antimony lead, tantalum, indium, palladium, tellurium, rhenium, iridium, aluminum, ru Themes, germanium, molybdenum, tungsten, zinc and the like can be used.

[0189] As a method for producing such a dispersion of fine metal particles, a metal phase in a liquid phase, such as a physical production method such as a gas evaporation method, a sputtering method, or a metal vapor synthesis method, a colloid method, or a coprecipitation method is used. Examples of the chemical production method include reducing metal ions to produce fine metal particles. However, preferred are JP-A-11-76800, JP-A-11-80647, JP-A-11-319538, and JP-A-2000-239853. Colloidal methods, JP-A-2001-254185, 2001-53028, 2001-35255, 2000-124157, 2000-123634, etc. It is a dispersion. An electrode is formed using these metal fine particle dispersions, the solvent is dried, and then heated to a shape in the range of 100 to 300 ° C, preferably 150 to 200 ° C, as necessary. Metal fine particles are thermally fused to form an electrode pattern having a desired shape.

[0190] As a method for forming an electrode, a method of forming an electrode using a known photolithographic method or a lift-off method from a conductive thin film formed using a method such as vapor deposition or sputtering using the above as a raw material, aluminum, copper, or the like There is a method of etching by forming a resist on the metal foil by thermal transfer, ink jet or the like. Alternatively, a conductive polymer solution or dispersion, a dispersion containing metal fine particles, or the like may be directly patterned by an ink-jet method, or may be formed from a coating film by lithography, laser abrasion, or the like. Further, a method of patterning a conductive ink or conductive paste containing a conductive polymer or fine metal particles by a printing method such as relief printing, intaglio printing, planographic printing, or screen printing can also be used.

[0191] The source electrode and the drain electrode are particularly preferably formed using a photolithographic method. In this case, a light-sensitive resin solution is applied to the entire surface of the layer in contact with the protective layer of the organic semiconductor, and light is applied. Form a sensitive resin layer.

[0192] As the photosensitive resin layer, the same positive and negative photosensitive resins used for patterning the protective layer can be used.

[0193] In the photolithographic method, after that, patterning is performed using a metal fine particle-containing dispersion or conductive polymer as a material for the source electrode and the drain electrode, and heat fusion is performed as necessary.

[0194] A solvent for forming a light-sensitive resin coating solution, a method for forming a light-sensitive resin layer, etc. As described in the patterning of the protective film.

The same applies to the light source used for patterning exposure after the formation of the photosensitive resin layer and the developer used to display the image of the photosensitive resin layer. In addition, an abrasion layer, which is another photosensitive resin layer, may be used for electrode formation. As the abrasion layer, the same ones as those used for patterning the protective layer can be mentioned.

[0196] Various insulating films can be used as the gate insulating layer of the organic thin film transistor of the present invention, and an inorganic oxide film having a high relative dielectric constant is particularly preferable. Examples of inorganic acids include silicon oxide, acid aluminum, acid tantalum, titanium oxide, tin oxide, vanadium oxide, barium strontium titanate, barium zirconate titanate, zirconate zirconate titanate, Examples include lanthanum titanate, strontium titanate, barium titanate, magnesium magnesium titanate, bismuth titanate, strontium bismuth titanate, strontium bismuth tantalate, bismuth tantalate niobate, and trioxide yttrium. Of these, preferable are silicon oxide, acid aluminum, acid tantalum, and acid titanium. Inorganic nitrides such as silicon nitride and aluminum nitride can also be suitably used.

[0197] Examples of the film formation method include vacuum deposition, molecular beam epitaxy, ion cluster beam, low energy ion beam, ion plating, CVD, sputtering, and atmospheric pressure plasma. Dry process, spray coating method, spin coating method, blade coating method, dip coating method, casting method, roll coating method, bar coating method, die coating method, and other methods by patterning such as printing and inkjet Etc., and can be used depending on the material.

[0198] The wet process includes a method of applying and drying a liquid in which fine particles of inorganic oxide are dispersed in an arbitrary organic solvent or water using a dispersion aid such as a surfactant as required, or an oxide precursor. A so-called sol-gel method in which a solution of a body, for example, an alkoxide body is applied and dried is used.

[0199] Among these, the above-mentioned atmospheric pressure plasma CVD method is preferable.

[0200] It is also preferable that the gate insulating layer is composed of an anodized film or the anodized film and an insulating film. The anodized film is preferably sealed. Anodized film can be anodized It is formed by anodizing an active metal by a known method.

[0201] Examples of the metal capable of anodizing treatment include aluminum and tantalum, and a known method with no particular limitation can be used for the method of anodizing treatment. An oxide film is formed by anodizing. Any electrolyte can be used as an electrolytic solution used for anodizing treatment as long as it can form a porous acid film. Generally, sulfuric acid, phosphoric acid, oxalic acid, chromic acid, boric acid, sulfamic acid, For benzene sulfonic acid, etc., a mixed acid or a salt thereof in which two or more of these are combined is used. The treatment conditions for anodization vary depending on the electrolyte used, and therefore cannot be specified. However, in general, the electrolyte concentration is 1 to 80% by mass, the electrolyte temperature is 5 to 70 ° C, the current is Density 0.5-60AZdm ² , voltage 1-: LOO volts, electrolysis time 10 seconds to 5 minutes are appropriate. A preferred anodizing treatment is a method in which an aqueous solution of sulfuric acid, phosphoric acid or boric acid is used as the electrolytic solution and the treatment is performed with a direct current, but an alternating current can also be used. The concentration of these acids is preferably 5 to 45% by weight. It is preferable to perform electrolytic treatment for ²⁰ to 250 seconds at an electrolyte temperature of 20 to 50 ° C and a current density of 0.5 to 20 A / dm ^2. Better!/,.

[0202] Further, as the organic compound film, polyimide, polyamide, polyester, polyacrylate, photo-radical polymerization system, photo-power thione polymerization system photocurable resin, or copolymer containing acrylonitrile component, polybule Phenolic alcohol, polybutyl alcohol, novolac resin, cyano ethyl pullulan, and the like can also be used.

[0203] The wet process is preferred as the method of forming the organic compound film.

[0204] The inorganic oxide film and the organic oxide film can be laminated and used together. The thickness of these insulating films is generally 50 nm to 3 μm, preferably 100 nm to 1 μm.

[0205] When an organic semiconductor is formed on the gate insulating layer, an arbitrary surface treatment may be performed on the surface of the gate insulating layer. Silane coupling agents such as octadecyltrichlorosilane, trimethylsilazane, and self-organized alignment films such as alkane phosphoric acid, alkanesulfonic acid, and alkanecarboxylic acid are preferably used.

[Substrate (also called substrate)]

Various materials can be used as the base material constituting the base, such as ceramic bases such as glass, quartz, aluminum oxide, sapphire, silicon nitride, silicon carbide, and the like. Power capable of using semiconductor substrates such as recon, germanium, gallium arsenide, gallium phosphide, gallium nitrogen, paper, nonwoven fabric, etc. In the present invention, the substrate is preferably made of resin. For example, a plastic film sheet is used. it can. Examples of the plastic film include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate (PC), Examples of such films include cellulose triacetate (TAC) and cellulose acetate propionate (CAP). By using a plastic film, it is possible to achieve a lighter weight than when a glass substrate is used, to improve portability and to improve resistance to impact.

[0207] A protective layer may be provided on the organic thin film transistor of the present invention. Examples of the protective layer include the above-described inorganic acid or inorganic nitride, and the protective layer is preferably formed by the above-mentioned atmospheric plasma method. Thereby, the durability of the organic thin film transistor is improved.

Example

[0208] Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto. Unless otherwise specified, “%” in the examples represents “mass%”.

[0209] Example 1

(Production of organic thin film transistor)

A 200-nm-thick thermal oxide film was formed on an n-type Si wafer having a specific resistance of 0.02 Ω'cm as a gate electrode to form a gate insulating layer. After the surface of the thermal oxide film is cleaned by oxygen plasma treatment, the following surface treatment agents A and B are mixed at a molar ratio shown in Table 1 and dissolved in a toluene solution (1% by mass, 55 ° C) for 10 minutes. After crushing, it was rinsed with toluene, dried, and surface-treated with a hot acid film.

[0210] A: Octyltrichlorosilane

B: 4-Phenylbutyltrichlorosilane

This surface treatment of Si on the wafer was performed, Exemplified Compound <9> hexane Z toluene cyclohexane was dissolved (organic semiconductor material) (0.2 mass ^_0/0, cyclohexane: toluene = 1: 1 Quality The ratio was applied using an applicator. After drying at room temperature, an organic semiconductor layer was formed by heat treatment at 50 ° C. for 30 minutes in a nitrogen gas atmosphere. The thickness of the organic semiconductor layer was 20 nm.

[0211] Further, gold was deposited on the surface of the film using a mask to form a source electrode and a drain electrode. Next, after heating at 90 ° C. for 1 minute in a nitrogen gas atmosphere, it was cooled to room temperature, and organic thin film transistors 11 to 16 having a channel width W = lmm and a channel length L = 30 μm were produced.

[0212] (Evaluation of organic thin film transistor)

The following evaluation was performed about the obtained organic thin-film transistor. The evaluation results are shown in Table 1.

The evaluation result is shown as an average value of the time when a uniform organic semiconductor layer was formed among the 10 coating trials.

[0213] <Measurement of contact angle>

The contact angle of water on the surface of the thermally treated oxide film was measured using a contact angle meter (CA—DT'A type: manufactured by Kyowa Interface Science Co., Ltd.) in an environment of 20 ° C. and 50% RH.

[0214] <Applicability>

The applicability during application of the organic semiconductor material solution was evaluated according to the following criteria.

[0215] ○: A uniform organic semiconductor layer was formed 10 times after 10 coating trials

Δ: A uniform organic semiconductor layer was formed 8 times for 10 coating trials.

[0216] X: After 10 trials, the organic semiconductor solution bounces 5 times, and the organic semiconductor layer is not formed.

The saturation region force carrier mobility of IV characteristics was calculated, and the onZoff ratio was calculated from the ratio of drain current values when the gate bias was 50 V and 0 V, with a drain bias of 50 V.

[0217] The organic thin film transistor 11 was unreliable for the average evaluation of the carrier mobility and the onZoff ratio, which had poor applicability.

[0218] [Table 1] Organic thin film Surface treatment agent 1 Surface treatment agent 2

After surface treatment

Transistor mobility

Quantity Applicability

Compound Compound Contact angle (degree) (cm v * on / o † f ratio ifm- s)

No. (Molar ratio) (Molar ratio)

11 A 100 B 0 105 X-Comparative example

12 A 80 a 20 99 ○ 0.20 3X10 ^{6 The} present invention

13 A 60 a 40 94 ○ 0.18 2X10 ^{6 The} present invention

14 A 40 a 60 90 ○ 0-12 1.5X10 ^{6 The} present invention

15 A 20 B 80 85 ○ 0.05 7X10 ⁵ This invention

16 A 0 B 100 72 O 0.002 2 0 ^ Comparative example

A: A talented clintil

B: 4-phenylbutyl trichlorosilane

[0219] The obtained organic thin film transistor, except for the organic thin film transistor 1, operated well as a p-channel enhancement type FET.

[0220] From the results in Table 1, the organic thin film transistors 11 and 16 of the comparative examples in which the surface of the substrate was treated with one type of surface treatment agent were strong enough to achieve both coating properties and TFT characteristics. The organic thin film transistors 12 to 15 of the present invention in which the surface of the substrate is treated with two kinds of surface treatment agents are as follows:

, Coating property, carrier mobility and onZoff were good.

[0221] Example 2

In the production of the organic thin film transistor of Example 1, the surface treatment agents A and B were changed to the following surface treatment agents C and D, and others were produced in the same manner to produce organic thin film transistors 21 to 26. The obtained organic thin film transistor was evaluated in the same manner as in Example 1. The results are shown in Table 2.

C: Hexyltrichlorosilane [0222] The organic thin film transistor 21 was poor in applicability and could not evaluate the carrier mobility and the onZoff ratio.

[0223] [Table 2] Yari Γ membrane Surface treatment agent 1 Surface treatment agent 2

After surface treatment

Transistor amount Dispensability on / of f ratio Remarks

No. Compounding base Contact angle (degree)

(Molar ratio) (Molar ratio)

2 1 C 100 D 0 103 X One Comparative example

22 C 80 D 20 98 ○ 0.24 4 X 10 ⁶ Present invention

23 C 60 D 40 90 ○ 0.22 3 X 10 ⁶ Present invention

24 G 40 D 60 87 0 0, 1 5 1 10 ⁶ Present invention

25 C 20 D 80 82 0 0, 07 6 X 10 ^{s The} present invention

26 C 0 D 100 68 ○ 0 .003 3 X \ 0 ^A Comparative example

C: Hexylto Riku □□ silane

D: 3—Phenoxypro'pyrto chlorosilane

[0224] From the results in Table 2, the organic thin film transistors 21 and 26 of the comparative examples in which the surface of the substrate was treated with one type of surface treatment agent were strong enough to achieve both coating properties and TFT characteristics. The organic thin film transistors 22 to 25 of the present invention in which the surface of the substrate was treated with two kinds of surface treating agents had good coating properties, carrier mobility and onZoff.

[0225] Example 3

(Production of organic thin film transistor)

^

A 200-nm-thick thermal oxide film was formed on an n-type Si wafer having a specific resistance of 0.02 Ω'cm as a gate electrode to form a gate insulating layer.

Furthermore, a toluene solution (1% by mass, publishing with helium gas) in which the following surface treatment agents E and F were mixed and dissolved at a molar ratio shown in Table 3 as a part of the reaction gas was further added. It was used and continuously subjected to atmospheric pressure plasma treatment (surface treatment) under the following conditions.

[0227] E: Octyltriethoxysilane

F: 4-Phenylbutyltriethoxysilane

Inert gas: helium 98.25 volume ^_0/0

Reactive gas: Oxygen gas 1. 50% by volume

Reactive gas: Steam of surface treatment agents E and F in toluene solution 0.25 vol%

Discharge output: lOWZcm ²

Here, discharge was performed at a frequency of 13.56 MHz using a high-frequency power source manufactured by Pearl Industries.

The electrode is against a stainless steel jacket roll base material that has cooling means with cooling water. Then, lmm is coated with alumina by ceramic spraying, and then a solution obtained by diluting tetramethoxysilane with ethyl acetate is applied and dried, then sealed with UV irradiation, and the surface is smoothed to make the surface Rmax 5 μm. This is a roll electrode with a relative dielectric constant of 10 and is grounded. On the other hand, as the application electrode, a hollow rectangular stainless steel pipe was covered with the same dielectric material under the same conditions.

[0229] This surface treatment on Si wafers was carried out, Exemplified Compound <9> hexane Z toluene cyclohexane was dissolved (organic semiconductor material) (0.2 mass ^_0/0, cyclohexane: toluene = 1: 1 mass ratio) was applied using an applicator. After drying at room temperature, an organic semiconductor layer was formed by heat treatment at 50 ° C. for 30 minutes in a nitrogen gas atmosphere. The thickness of the organic semiconductor layer was 20 nm.

[0230] Further, gold was deposited on the surface of the film using a mask to form a source electrode and a drain electrode. Next, after heating at 90 ° C. for 1 minute in a nitrogen gas atmosphere, it was cooled to room temperature, and organic thin film transistors 31 to 36 having a channel width W = lmm and a channel length L = 30 μm were produced.

[0231] The obtained organic thin film transistor was evaluated in the same manner as in Example 1. The results are shown in the table

Shown in 3.

[0232] [Table 3]

Ε: A talented knight

F: 4-phenylbutyltriethoxysilane

[0233] From the results in Table 3, the organic thin film transistors 21 and 26 of the comparative examples in which the surface of the substrate was treated with one type of surface treatment agent had insufficient TFT characteristics. The organic thin film transistors 32 to 35 of the present invention in which the surface of the substrate was treated with two kinds of surface treating agents had good carrier mobility and onZoff.

Claims

The scope of the claims

[I] An organic thin film transistor having a substrate and an organic semiconductor layer on the surface thereof, and having a surface treatment layer formed of 2 to 5 types of surface treatment agents on the substrate surface between the organic semiconductor layer and the substrate An organic thin film transistor characterized by the above.

[2] The organic thin film transistor according to [1], wherein the surface treatment agent is a silane compound.

[3] The organic thin film transistor according to [2], wherein at least one of the surface treatment agents is a silane compound having an alkyl group.

[4] The organic thin film transistor according to [2], wherein at least one of the surface treatment agents is a silane compound having an aromatic group.

[5] According to claim 2, wherein at least one of the surface treatment agents is a silane compound having an alkyl group, and at least one is a silane compound having an aromatic group. The organic thin-film transistor as described.

6. The organic thin film transistor substrate according to any one of claims 1 to 5, wherein a contact angle of the surface of the surface-treated substrate with respect to water is 50 degrees or more.

7. The organic thin film transistor according to any one of claims 1 to 5, wherein the organic semiconductor material contained in the organic semiconductor layer has an alkyl group.

[8] The organic thin film transistor according to any one of claims 1 to 5 and 7, which has a bottom gate structure.

[9] The method of producing an organic thin film transistor according to any one of claims 1 to 5, 7, and 8, wherein the surface treatment is performed by supplying a solution of the surface treatment agent to the surface of the substrate. The manufacturing method of the organic thin-film transistor characterized by performing.

[10] The method of manufacturing an organic thin film transistor according to any one of claims 1 to 5, 7, and 8, wherein the surface treatment is performed by a plasma CVD method using the surface treatment agent. A method for producing a featured organic thin film transistor.

[I I] The method of manufacturing an organic thin film transistor according to claim 10, wherein the plasma CVD method is an atmospheric pressure plasma CVD method.

[12] The method for producing an organic thin film transistor according to any one of claims 9 to 11 An organic thin film transistor manufactured by: